EP0643326B1 - Neuer Typ von Polymerlatex und sein Verwendung als Weichmacher in einem photographischen Material - Google Patents

Neuer Typ von Polymerlatex und sein Verwendung als Weichmacher in einem photographischen Material Download PDF

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Publication number
EP0643326B1
EP0643326B1 EP19940202261 EP94202261A EP0643326B1 EP 0643326 B1 EP0643326 B1 EP 0643326B1 EP 19940202261 EP19940202261 EP 19940202261 EP 94202261 A EP94202261 A EP 94202261A EP 0643326 B1 EP0643326 B1 EP 0643326B1
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Prior art keywords
polymer
acid
radical
photographic material
polymer latex
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French (fr)
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EP0643326A1 (de
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Michael c/o Agfa-Gevaert N.V. Müller
Daniel M. C/O Agfa-Gevaert N.V. Timmerman
Guido Vital C/O Afga-Gevaert N.V. Desie
Stefaan Frans C/O Afga-Gevaert N.V. Lingier
Günter c/o Afga-Gevaert N.V. Sackmann
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion

Definitions

  • the present invention relates to new types of polymeric latices and their use in photographic materials.
  • Coated photographic layers and complete photographic materials must comply with a number of requirements concerning physical properties. In order to avoid physical damage during manufacturing and handling a photographic material must show a sufficiently high scratch resistance. Furtheron, photographic materials must show a good flexibility so that easy handling without the occurence of creases or cracks is possible ; in other words, the materials may not suffer from brittleness especially under critical low humidity conditions. On the other hand, stickiness should be avoided. Still furtheron, photographic materials must show a good dimensional stability, meaning a minimal dimensional distortion during processing especially during the drying phase at elevated temperature. The requirement of dimensional stability is particularly stringent for graphic arts contact materials often serving in pre-press activity as final intermediates between colour separations produced on a scanner and the exposure step onto a printing plate. Several contacts, being duplicates of different separations, have to be exposed in register on one and the same printing plate and mutually different dimensional distortions would lead to unacceptable colour shifts on image edges in the final print.
  • plasticizers include alcohols, dihydric alcohols, trihydric alcohols and polyhydric alcohols, acid amides, cellulose derivatives, lipophilic couplers, esters, phosphate esters such as tricresyl phosphate, glycol esters, diethylene glycol mixed esters, phthalate esters such as dibutyl phthalate and butyl stearate, tetraethylene glycol dimethyl ether, ethyl acetate copolymers, lactams, lower alkyl esters of ethylene bis-glycolic acid, esters or diesters of an alkylene glycol or a polyalkylene glycol, polyacrylic acid esters, polyethylene imines, poly(vinyl acetate) and polyurethanes, as illustrated by Eastman et al U.S.
  • Low-molecular plasticizers with hydrophilic groups show the disadvantage of rendering the coated hydrophilic layer(s) of a photographic element sticky particularly at elevated relative humidity.
  • photographic materials are packaged, stored and delivered in a web-like or sheet-like manner an unacceptable adherance of support parts to surface parts can occur during storage or after processing. Moreover, they are not diffusion resistant.
  • plasticizers consisting of conventional polymer latices, e.g. polyethylacrylates and analogues which are widely used in commercial materials, show other drawbacks.
  • the amount of latex which can be incorporated in a gelatinous layer in order to improve dimensional stability is limited because high concentrations of the latex disturb the cohesion of the gelatine matrix resulting in a decrease of the scratch resistance eventually below a critical level.
  • a method for the preparation of stable equeous dispersions of finely divided solid spherical polymer beads having an average size between about 0.5 and about 5 ⁇ m and having a glass transition temperature of at least 40°C by dissolving in an aqueous solvent mixture at least one ⁇ , ⁇ -ethylenically unsaturated monomer capable of forming a polymer that is soluble in the monomer(s) present in said aqueous solvent mixture but which is insoluble in said aqueous solvent mixture, a free radical-forming polymerization initiator, and a graft-polymerizable polymer containing hydrophilic groups, heating the solution to a temperature from 50°C to the reflux temperature thereof with stirring go as to form said polymer beads.
  • the resulting dispersion shows a total absence of any polymeric fraction in latex form.
  • the present invention extends the teachings on improved polymer latices for use as plasticizers in photographic materials.
  • a photographic material comprising a support, at least one silver halide emulsion layer, and optionally one or more other hydrophilic layer(s), characterized in that at least one of said emulsion or other hydrophilic layer(s) contains a polymer latex with an average particle size of less than 500 nm, which is obtained by subjecting to radical emulsion polymerisation one or more radical-polymerisable monomers, whose emulsifier-free homopolymers or copolymers possess a glass transition temperature below 65 °C, preferably below 30 °C, in the presence of a water-soluble polymer of formula I wherein
  • the polymers I.1 are known (DE 3344470, DE 3807097, DE 3429961, DE 3609981, DE 3703551, DE 3331542, EP 0 307 778, EP 0 009 185, DE4034871, US 4,151,336, J. Am. Chem. Soc. Vol. 68 (1946) p. 1495, J. Macromol. Sci.-Chem. Vol. A6(8) (1972) p. 1459, J. Macromol. Sci.-Chem. Vol. A4(1) (1970) p. 51).
  • the polymers I.2 can be prepared in a similar way from known copolymers of maleic acid anhydride and furan (See J. Am. Chem. Soc. Vol. 68 (1946) p. 1495, J. Macromol. Sci.-Chem. Vol. A6(8) (1972) p. 1459, J. Macromol. Sci.-Chem. Vol. A4(1) (1970) p. 51, both cited above) by the ring splitting reagents III.
  • Suitable polymers I.1 are, e.g.: (mixture wherein the sum of R', R" and R′′′ represents -C 7 H 17 )
  • a suitable polymer I.2 is :
  • (meth)acrylic acid esters within the scope of this invention are to be understood esters of methacrylic- and acrylic acid. Suitable (meth)acrylic acid esters are, e.g.:
  • vinyl monomers that contain carboxylate groups or sulphonate groups or that are capable of forming them by a variation of the pH.
  • examples of preferred vinyl monomers of this kind are
  • Especially preferred vinyl monomers with anionic groups are 2-propenoic acid sodium salt and N-1,1-dimethyl-2-sulphoethyl acrylamide sodium salt.
  • mixtures according to the invention of radical-polymerisable monomers can contain such vinyl monomers up to 25 % by weight, preferably 0.5 to 15 % by weight, which are capable of reacting with gelatine or with gelatine hardeners that are of common use in photographic layers.
  • Inorganic peroxides such as hydrogen peroxide, potassium peroxodisulphate and ammonium peroxodisulphate are suited as well.
  • the initiators decomposing in radicals can be used alone or in combination with reducing agents or heavy metal compounds.
  • Such compounds are, e.g., sodium- or potassium pyrosulphite, formic acid, ascorbic acid, thiourea, hydrazine- or amine derivatives and RONGALIT (1-hydroxymethanesulphinic acid Na-salt).
  • the heavy metal compounds can be present in oil-soluble as well as in water-soluble form.
  • water-soluble heavy metal compounds are silver nitrate, halides and sulphates of 2- and 3-valent iron, cobalt, nickel and salts of titanium or vanadium in low valency stages.
  • oil-soluble heavy metal compounds are cobalt naphthenate and the acetylacetone complexes of vanadium, cobalt, titanium, nickel and iron.
  • the emulsion polymerisations take place at temperatures between 20 and 100 °C, preferably between 40 and 85 °C.
  • the amount of other emulsifying agents that can be used in addition to the polymers I is 0 to 20 %, preferably 1 to 5 %, based on the monomers to be polymerised.
  • Anionic as well as non-ionic emulsifying agents are suited therefore.
  • Carrying out the emulsion polymerisation can take place in such a way that an aqueous solution of polymer I, optionally together with other emulsifying agents, is prepared and then the monomers and the initiator are fed separately. It is also possible, however, to prepare only a part of polymer I in water, optionally together with other emulsifying agents and to feed the remainder together with the monomers, the initiator and optionally additional emulsifying agents in separate fluxes. Alternatively, one can proceed in such a way that an aqueous solution of polymer I, monomers, initiator and optionally other emulsifying agents are fed continuously or intermittently over the entire period of polymerisation and that only a determined amount of water is used.
  • emulsion polymerisation only a part of the monomers is first polymerised according to a batch-wise process, whereupon further monomers are fed, occasionally together with initiator and emulsifying agent.
  • the applied and dropwise added monomer (mixture) can then be composed differently.
  • polymer I is being applied as an aqueous solution, it may be advantageous for the polymerisation to heat the receiver together with the initiator to 40 to 85 °C for some time, e.g. between 10 and 180 min, before adding the monomers.
  • an aqueous solution of polymer I together with potassium peroxidisulphate is prepared.
  • the preparation is heated at 65 °C with stirring for some time, whereupon first an aqueous solution of a low-molecular emulsifying agent is added at once and then the monomer mixture within some period of time.
  • the mixture is stirred at increased temperature, demonomerised at 90 °C under reduced pressure, cooled and mixed with a 20 % solution of 1000 ppm of phenol in ethanol/water (1:1).
  • the type of photographic material in which the polymer latices are incorporated according to the present invention and its field of use is not limited in any way. It includes photographic elements for graphic arts and for so-called amateur and professional black-and-white or colour photography, cinematographic recording and printing materials, X-ray diagnosis, diffusion transfer reversal photographic elements, low-speed and high-speed photographic elements, etc.
  • photographic elements for graphic arts and for so-called amateur and professional black-and-white or colour photography cinematographic recording and printing materials
  • X-ray diagnosis X-ray diagnosis
  • diffusion transfer reversal photographic elements low-speed and high-speed photographic elements, etc.
  • the advantages of the present invention become most perspicuous when the latices are incorporated in photographic materials setting high standards to dimensional stability, e.g. graphic arts contact materials as explained in the background section.
  • Several types of commercial contact materials are available.
  • Duplicating materials can be of the classical dark room type but in recent times preference is given to so-called daylight or roomlight contact materials which can be handled for a reasonable period under UV-poor ambient light. Also yellow light contact materials exist which can be handled under relative bright yellow light. Very insensitive daylight types are available which have to be exposed by strongly emitting metal-halogen sources. Less insensitive types are designed for exposure by quartz light sources. The daylight materials can be of the negative working type or of the direct positive working type.
  • the silver halide emulsion layer simply consists of just one layer. However double layers and even multiple layer packs are possible.
  • a photographic element usually comprises several non-light sensitive layers, e.g. protective layers, backing layers, filter layers and intermediate layers (or "undercoats"). All of these layers can be single, double or multiple.
  • the polymer latices of the present invention can be present in all these layers, or in several of them, or in just one of them. In principle a mixture of two or more different latices can be used, or an invention latex can be mixed with a conventional plasticizer, but for normal practice just one representative of the new types will be sufficient.
  • the plasticizer is preferably present in the emulsion layer in a plasticizer/gelatin ratio ranging from 0.2 to 1.
  • the preferred ratio range is between 0.2 and 1 equally.
  • composition of the silver halide emulsion incorporated in a photographic element of the present invention is not specifically limited and may be any composition selected from e.g. silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
  • a contact material especially a daylight material, emulsions rich in chloride are preferred.
  • the photographic emulsion(s) can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1967), by G.F. Duffin in “Photographic Emulsion Chemistry", The Focal Press, London (1966), and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966).
  • the average size of the silver halide grains may range from 0.05 to 1.0 ⁇ m, preferably from 0.2 to 0.5 ⁇ m. For daylight materials the average grain size is preferably comprised between 0.07 ⁇ m and 0.20 ⁇ m.
  • the size distribution of the silver halide particles can be homodisperse or heterodisperse.
  • the light-sensitive silver halide emulsions can be chemically sensitized as described e.g. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkidès, in the above-mentioned “Photographic Emulsion Chemistry” by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • the emulsion is preferably not chemically ripened and preferably contains relative high amounts of a desensitizer.
  • the light-sensitive silver halide emulsions can be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • the emulsion is preferably not spectrally sensitized in view of the daylight stability.
  • the silver halide emulsion(s) for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof. Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion.
  • the photographic material of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in another hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g.
  • polyethylene glycol polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • the support of the photographic material can be a transparent base, preferably an organic resin support, e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly-alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a subbing layer.
  • the support of the photographic material can be a paper base preferably a polyethylene or polypropylene coated paper base.
  • the photographic material can be exposed according to its particular composition and application, and processed by any means or any chemicals known in the art depending on its particular application.
  • the used polymers I are copolymers that are composed alternatingly to a wide extent, if not stated otherwise.
  • the mixture was stirred at 65 °C for another 16 h, cooled, mixed with a 20 % solution of 1000 ppm of phenol in ethanol/water (1:1) and filtered through a 100- ⁇ m filter.
  • the obtained latex had a solids content of 21.9 % (w/w), a pH of 6.6 and according to laser correlation spectroscopy an average particle size of 75 nm.
  • the mixture was stirred at 65 °C for another 16 h, cooled, mixed with a 20 % solution of 1000 ppm of phenol in ethanol/water (1:1) and filtered through a 100- ⁇ m filter.
  • the obtained latex had a solids content of 21.6 % (w/w), a pH of 6.4 and according to laser correlation spectroscopy an average particle size of 133 nm.
  • the obtained latex had a solids content of 22.0 % (w/w), a pH of 5.7 and according to laser correlation spectroscopy an average particle size of 61 nm.
  • the obtained latex had a solids content of 22.7 % (w/w), a pH of 5.7 and according to laser correlation spectroscopy an average particle size of 82 nm.
  • the obtained latex had a solids content of 21.6 % (w/w), a pH of 6.7 and according to laser correlation spectroscopy an average particle size of 79 nm.
  • the latex formed was degassed under reduced pressure at 60 °C and filtered through a 100- ⁇ m cloth. It had a solids content of 23.5 % and according to laser correlation spectroscopy an average particle size of 52 nm.
  • 100 g of a terpolymer which in a first stage was prepared from 50 mol-% of maleic anhydride, 44 mol-% of ⁇ -diisobutylene and 6 mol-% of styrene and thereupon was reacted with an amount of sodium taurinate equimolar to that of the maleic anhydride, were dissolved in 2275 g of water and mixed with 10 g of potassium peroxidisulphate under nitrogen atmosphere.
  • the preparation was heated at 65 °C with stirring for 1 h and then at the same time a monomer mixture consisting of 111.65 g of ethyl acrylate, 135.9 g of methyl methacrylate and 2.5 g of acrylic acid as well as 36.25 g of a 3.45 % aqueous solution of potassium peroxidisulphate was added in 5 min.
  • the mixture was stirred at 80 °C for another h, demonomerised at 90 °C, then cooled and mixed with a 20 % solution of 1000 ppm of phenol in ethanol/water.
  • the pH of the obtained latex was increased from 4.5 to 5.5 by adding 25 ml of 1 N sodium hydroxide solution.
  • the latex had a solids content of 26.7 % (w/w) and according to laser correlation spectroscopy an average particle size of 78 nm.
  • the pH of the obtained latex was 4.8 and was increased to 5.5 by adding 20 ml of 1 N sodium hydroxide solution.
  • the latex had a solids content of 26.4 % (w/w) and according to laser correlation spectroscopy an average particle size of 286 nm.
  • 3340 g of an aqueous solution containing 25 g of polymer Ia-1 and 10 g of potassium peroxidisulphate was prepared under nitrogen atmosphere. This solution was heated at 65 °C with stirring for 2 h and thereupon at once 150 ml of 1 N sodium hydroxide solution and 400 ml of a 10 % aqueous solution of HOSTAPON T were added. Thereupon the monomer mixture consisting of 990 g of ethyl acrylate and 10 g of acrylic acid was added within 15 min.
  • the obtained latex had a solids content of 22.7 % (w/w), a pH of 5.6 and according to laser correlation spectroscopy an average particle size of 129 nm.
  • the obtained latex had a solids content of 22.2 % (w/w), a pH of 5.9 and according to laser correlation spectroscopy an average particle size of 108 nm.
  • the obtained latex had a solids content of 22.3 % (w/w), a pH of 5.8 and according to laser correlation spectroscopy an average particle size of 89 nm.
  • the obtained latex had a solids content of 21.7 % (w/w), a pH of 6.1 and according to laser correlation spectroscopy an average particle size of 86 nm.
  • 3340 g of an aqueous solution containing 25 g of polymer Ia-1 and 10 g of potassium peroxidisulphate was prepared under nitrogen atmosphere. This solution was mixed at once with 150 ml of 1 N sodium hydroxide solution and 400 ml of a 10 % aqueous solution of HOSTAPON T. Thereupon the monomer mixture consisting of 446.5 g of butyl acrylate, 543.5 g of methyl methacrylate and 10 g of acrylic acid was added within 15 min.
  • the obtained latex had a solids content of 19.8 % (w/w), a pH of 6.3 and according to laser correlation spectroscopy an average particle size of 74 nm.
  • the photographic material was prepared as follows. A direct positive pure silver bromide emulsion was precipitated by a double jet technique and internally sensitized. The emulsion was then externally fogged using thiourea dioxide as to obtain the desired sensitivity. Finally the emulsion was divided in aliquot portions and different latices were added to each portion according to table 1.
  • the coating solutions thus prepared were applied to a subbed polyethylene terephtalate base at a silver coverage, expressed as silver nitrate, of 3.18 g/m 2 , and a gelatin coverage of 2.7 g/m 2 .
  • a protective layer was applied containing gelatin hardened with formaldehyde at a coverage of 0.7 g/m 2 .
  • the sensitivity and gradation were determined as follows.
  • the coated samples were exposed to an UV-white light source (AGFA CDL 2001S) and developed in a conventional Phenidone-hydroquinone developing solution (AGFA G4000), fixed, washed and dried in an AGFA RAPILINE 66A processor.
  • the direct positive sensitivity was determined at density 0.1 above minimum density and expressed as relative log H value, higher figure meaning higher sensitivity.
  • the gradation was measured as the slope of the linear part of the sensitometric curve.
  • the scratch resistance was measured by scratching the coated samples with a ball point under a gradually increasing load.
  • the value of the scratch resistance corresponds to the load in grams required for cutting through the emulsion layer completely.
  • the dimensional change during processing is evaluated as follows. Each coated sample was conditioned in an acclimated room for at least 6 hours to a relative humidity of 30 or 60 % respectively at 22 °C. Two holes with a diameter of 5 mm were punched at a distance of 200 mm in each film sample having dimensions of 35 mm x 296 mm. The exact interval between those holes was measured with an inductive half-bridge probe (TESA FMS100) having an accuracy of 1 ⁇ m, whereby this distance was called X ⁇ m. Subsequently the film material was subjected to processing in an automatic apparatus, a PAKO 26RA the dryer of which was equipped with an air-inlet.
  • TSA FMS100 inductive half-bridge probe
  • the samples were developed at 38 °C, fixed at 33 °C, rinsed without temperature control, and dried, whereby air of 22 °C and of 30 % RH or of 60 % RH respectively was provided through the air-inlet and wherby the temperature was raised upto 35 °C in the case of 60 % RH, or 55 °C in the case of 30 % RH.
  • the distance between the two holes in the film is measured again after an acclimatisation period of 3 hours and is expressed as Y ⁇ m.
  • the dimensional stability is calculated as (Y-X).5 and expressed in ⁇ m/m.
  • the silver bromide emulsion was prepared as in example 1.
  • the respective latices were added to the emulsion in an amount corresponding to a coverage of 1.5 g/m 2 after coating.
  • the coating solutions were applied to a polyethylene terephtalate base at a coverage of 3.18 Ag/m 2 and 1.5 g gelatin/m 2 .
  • the same protective layer was applied as in example 1.
  • the silver bromide emulsion was prepared as in example 1.
  • the respective latices were added to the emulsion in an amount corresponding to a coverage of 1.5 g/m 2 after coating.
  • the coating solutions were applied to a polyethylene terephtalate base at a coverage of 3.18 Ag/m 2 and 1.5 g gelatin/m 2 .
  • the protective layer was applied containing formaldehyde hardened gelatin at a coverage of 0.7 g/m 2 and a latex at a coverage of 1.4 g/m 2 .

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Claims (12)

  1. Fotografisches Material, das einen Träger, wenigstens eine Silberhalogenid-Emulsionsschicht und gegebenenfalls eine oder mehrere hydrophile Gelatineschichten enthält, dadurch gekennzeichnet, daß wenigstens eine der Emulsionen oder anderen hydrophilen Gelatineschichten einen Polymerlatex mit einer mittleren Teilchengröße von weniger als 500 nm enthält, der dadurch erhältlich ist, daß man ein oder mehrere radikalisch polymerisierbare Monomere, deren emulgatorfreie Homopolymerisate oder Copolymerisate einen Einfrierpunkt unter 65°C aufweisen, in Gegenwart eines wasserlöslichen Polymerisates der Formel I
    Figure 00380001
    in der :
    Z - CH2 - CR1R2 - oder
    Figure 00380002
    ist,
    M H, Na, K, Li oder NH4 bedeutet,
    R1 H oder CH3 bedeutet,
    R2 H, eine substituierte oder nicht-substituierte C1-C6-Alkylgruppe, eine substituierte oder nicht-substituierte Arylgruppe, eine -(CH2)m-OCO-R5-Gruppe, in der R5 eine C1-C8-Alkylgruppe ist und m 0 oder 1 ist, oder
    Figure 00380003
    bedeutet,
    A OM, OR3, NH2, NHR3, O-R4-(SO3M)n oder NH-R4-(SO3M)n bedeutet, wobei R3 eine C1-C4-Alkylgruppe und R4 einen alifatischen oder aromatischen Rückstand mit 1 bis 10 Kohlenstoffatomen bedeutet und n 1 oder 2 ist, und
    x und y so gewählt werden, daß das Gewichtsmittel des Molekulargewichts des Polymerisates I zwischen 5.000 und 500.000 liegt und das Verhältnis x:y zwischen 1:4 und 1:1 liegt,
    einer radikalischen Emulsionspolymerisation unterwirft.
  2. Fotografisches Material nach Anspruch 1, dadurch gekennzeichnet, daß R2 -CH3, -C2H5, -C4H9, -CH2C(CH3)3), eine Phenylgruppe oder eine Tolylgruppe ist.
  3. Fotografisches Material nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß R4 von einem Rückstand aus der Gruppe bestehend aus C1-C4-Alkan, Benzol, Methylbenzol und Naphthalin abgeleitet ist.
  4. Fotografisches Material nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die radikalisch polymerisierbaren Monomeren ein Gemisch aus n.-Butylacrylat, Methylmethacrylat und Acrylsäure enthalten.
  5. Fotografisches Material nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Polymerlatex in einem Latex/Gelatine-Verhältnis zwischen 0,2 und 1 in der Emulsionsschicht und/oder der Schutzschicht enthalten ist.
  6. Fotografisches Material nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Material ein Kontaktkopiermaterial für den grafischen Bereich ist.
  7. Fotografisches Material nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das (die) radikalisch polymerisierbare(n) Monomere(n) (ein) Monomere(s) ist (sind), dessen (deren) emulgatorfreie Homopolymerisate oder Copolymerisate einen Einfrierpunkt von weniger als 30°C aufweisen.
  8. Polymerlatex mit einer mittleren Teilchengröße von weniger als 500 nm, der dadurch erhältlich ist, daß man ein oder mehrere radikalisch polymerisierbare Monomere, deren emulgatorfreie Homopolymerisate oder Copolymerisate einen Einfrierpunkt unter 65°C aufweisen, in Gegenwart eines wasserlöslichen Polymerisates der Formel I
    Figure 00400001
    in der :
    Z - CH2 - CR1R2 - oder
    Figure 00400002
    ist,
    M H, Na, K, Li oder NH4 bedeutet,
    R1 H oder CH3 bedeutet,
    R2 H, eine substituierte oder nicht-substituierte C1-C6-Alkylgruppe, eine substituierte oder nicht-substituierte Arylgruppe, eine -(CH2)m-OCO-R5-Gruppe, in der R5 eine C1-C8-Alkylgruppe ist und m 0 oder 1 ist, oder
    Figure 00400003
    bedeutet,
    A OM, OR3, NH2, NHR3 oder O-R4-(SO3M)n bedeutet, wobei R3 eine C1-C4-Alkylgruppe und R4 einen alifatischen oder aromatischen Rückstand mit 1 bis 10 Kohlenstoffatomen bedeutet und n 1 oder 2 ist, und
    x und y so gewählt werden, daß das Gewichtsmittel des Molekulargewichts des Polymerisates I zwischen 5.000 und 500.000 liegt und das Verhältnis x:y zwischen 1:4 und 1:1 liegt,
    einer radikalischen Emulsionspolymerisation unterwirft.
  9. Polymerlatex nach Anspruch 8, dadurch gekennzeichnet, daß R2 -CH3, -C2H5, -C4H9, -CH2C(CH3)3), eine Phenylgruppe oder eine Tolylgruppe ist.
  10. Polymerlatex nach Anspruch 8, dadurch gekennzeichnet, daß R4 von einem Rückstand aus der Gruppe bestehend aus C1-C4-Alkan, Benzol, Methylbenzol und Naphthalin abgeleitet ist.
  11. Polymerlatex nach Anspruch 10, dadurch gekennzeichnet, daß die radikalisch polymerisierbaren Monomeren ein Gemisch aus n.-Butylacrylat, Methylmethacrylat und Acrylsäure enthalten.
  12. Polymerlatex nach irgendeinem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß das (die) radikalisch polymerisierbare(n) Monomere(n) (ein) Monomere(s) ist (sind), dessen (deren) emulgatorfreie Homopolymerisate oder Copolymerisate einen Einfrierpunkt von weniger als 30°C aufweisen.
EP19940202261 1993-09-09 1994-08-05 Neuer Typ von Polymerlatex und sein Verwendung als Weichmacher in einem photographischen Material Expired - Lifetime EP0643326B1 (de)

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EP0790526B1 (de) 1996-02-19 2002-07-24 Agfa-Gevaert System von Film und Schirm zur Herstellung radiographischen Bildes
US5998118A (en) * 1998-02-05 1999-12-07 Eastman Kodak Company Backside protective overcoat compositions for silver halide photographic elements
GB0116682D0 (en) * 2001-07-07 2001-08-29 Eastman Kodak Co Black and white photographic material

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DE3265276D1 (en) * 1981-11-23 1985-09-12 Agfa Gevaert Nv Method for the preparation of stable aqueous dispersions of polymer beads and the use of these dispersions in photographic elements
DE3331542A1 (de) * 1983-09-01 1985-03-21 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches silberhalogenidaufzeichnungsmaterial
DE3516466C2 (de) * 1985-05-08 1995-03-23 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial mit einem polymeren Gelatineweichmacher
DE3807097A1 (de) * 1988-03-04 1989-09-14 Bayer Ag Polymerisate
JP2681163B2 (ja) * 1988-07-07 1997-11-26 コニカ株式会社 ハロゲン化銀カラー写真感光材料
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